KR970027125A - Process for preparing styrene and butadiene polymers - Google Patents

Process for preparing styrene and butadiene polymers Download PDF

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Publication number
KR970027125A
KR970027125A KR1019950044343A KR19950044343A KR970027125A KR 970027125 A KR970027125 A KR 970027125A KR 1019950044343 A KR1019950044343 A KR 1019950044343A KR 19950044343 A KR19950044343 A KR 19950044343A KR 970027125 A KR970027125 A KR 970027125A
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South Korea
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group
carbon atoms
alkyl
independently
general formula
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KR1019950044343A
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Korean (ko)
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KR100194004B1 (en
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박영환
박재현
오재승
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성재갑
주식회사 Lg 화학
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Priority to KR1019950044343A priority Critical patent/KR100194004B1/en
Publication of KR970027125A publication Critical patent/KR970027125A/en
Priority to KR1019980046211A priority patent/KR100204727B1/en
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Publication of KR100194004B1 publication Critical patent/KR100194004B1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F36/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

본 발명은 스티렌계 단량체와 부타디엔계 중합체를 제조하는 방법으로서, 새로운 구조의 제4족 전이 금속 촉매의 존재하에 조촉매로서 알킬 알루미늄 또는 알루미녹산을 단독 또는 혼합 사용하며, 보다 높은 촉매 활성하에서 효율적으로 중합체를 제조할 수 있다.The present invention provides a method for producing a styrene-based monomer and a butadiene-based polymer, using alkyl aluminum or aluminoxane alone or mixed as a cocatalyst in the presence of a Group 4 transition metal catalyst having a novel structure, and efficiently under higher catalytic activity. Polymers can be prepared.

Description

스티렌계 및 부타디엔계 중합체의 제조 방법Process for preparing styrene and butadiene polymers

본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음As this is a public information case, the full text was not included.

Claims (9)

조촉매로서 알킬 알루미늄 또는 알킬 알루미녹산을 단독 또는 혼합사용하면서 하기 일반식(1)의 제4족 전이 금속 촉매를 사용하는 것을 특징으로 하는 스티렌계 및 부타디엔계 중합체의 제조 방법:A method for producing a styrene-based butadiene-based polymer characterized by using a Group 4 transition metal catalyst of the following general formula (1) while using alkyl aluminum or alkyl aluminoxane alone or in combination as a cocatalyst: 상기 식에서, M은 제4족전이금속이고, R1,R2, R3, R4및 R5는 각각 독립적으로 수소, 할로겐원소, -OR10, -NR11 2(여기서, R10과 R11은 각각 독립적으로 탄소수 1 내지 20의 알킬기, 아릴기, 아릴알킬기 또는 알킬아릴기이다), 또는 탄소수 1 내지 20의 알킬기이고, 이들 중 인접한 2개는 탄소수 3 내지 5의 탄소 사슬 고리를 형성할 수 있으며, X1과 X2는 각각 독립적으로 일반식 AIR6R7R8R9(여기에서, R6, R7, R8및 R9는 각각 독립적으로 할로겐 원소, 탄소수 1 내지 10의 알킬기 또는 탄소수 1 내지 8의 알콕시기이다)이다.Wherein M is a Group 4 transition metal, and R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, a halogen element, -OR 10 , -NR 11 2 , wherein R 10 and R 11 are each independently C 1 -C 20 alkyl group, an aryl group, an arylalkyl group or alkylaryl group), or an alkyl group having 1 to 20 carbon atoms, and two adjacent ones of them to form a carbon chain ring of 3 to 5 carbon atoms X 1 and X 2 are each independently of the general formula AIR 6 R 7 R 8 R 9 (wherein R 6 , R 7 , R 8 and R 9 are each independently a halogen element, an alkyl group having 1 to 10 carbon atoms Or an alkoxy group having 1 to 8 carbon atoms. 제1항에 있어서, 스티렌계 단량체가 하기 일반식(2)를 갖는 것을 특징으로 하는 방법:The method according to claim 1, wherein the styrenic monomer has the following general formula (2): 상기 식에서, R12는 수소: 할로겐 원소: 또는 탄소, 산소, 질소, 황, 인 또는 규소를 포함하여 구성되고, 수소를 제외한 원자의 수가 1 내지 10인 치환기이다.Wherein R 12 is hydrogen: a halogen element: or a substituent comprising carbon, oxygen, nitrogen, sulfur, phosphorus or silicon and having 1 to 10 atoms excluding hydrogen. 제1항에 있어서, 부타디엔계 단량체가 하기 일반식(3)을 갖는 것을 특징으로 하는 방법.The method according to claim 1, wherein the butadiene monomer has the following general formula (3). 상기 식에서, R13내지 R16은 각각 독립적으로 수소, 할로겐 원소, 시안화기, 탄소수 1 내지 10의 알킬기, 알릴기, 알콕시기이다.In the above formula, R 13 to R 16 are each independently hydrogen, a halogen element, a cyanide group, an alkyl group having 1 to 10 carbon atoms, an allyl group, or an alkoxy group. 제1항에 있어서, 상기 알킬 알루미늄의 알킬기가 메틸기, 에틸기, 프로필기, 이소프로필기 또는 이소부틸기인 것을 특징으로 하는 방법.The method according to claim 1, wherein the alkyl group of the alkyl aluminum is a methyl group, an ethyl group, a propyl group, an isopropyl group or an isobutyl group. 제1항에 있어서, 상기 조촉매의 알루미늄 당량([A1])과 촉매 전구체의 당량([M])의 비([A1]/[M])가 1 내지 100,000인 것을 특징으로 하는 방법.The method according to claim 1, wherein the ratio ([A1] / [M]) of the aluminum equivalent ([A1]) of the cocatalyst to the equivalent ([M]) of the catalyst precursor is 1 to 100,000. 제1항에 있어서, 중합 반응을 -50 내지 110℃에서 진행시킴을 특징으로 하는 방법.The process according to claim 1, wherein the polymerization is carried out at -50 to 110 ° C. 제1항에 있어서, 중합 반응이 무용매 상태에서 진행됨을 특징으로 하는 방법.The method of claim 1 wherein the polymerization reaction proceeds in a solventless state. 제7항에 있어서, 상기 중합 반응이 1 내지 50기압하에서 진행됨을 특징으로 하는 방법.8. The process according to claim 7, wherein the polymerization reaction proceeds under 1 to 50 atmospheres. 제1항에 있어서, 중합 반응을 탄소수 4 내지 20의 지방족, 지환족 및 방향족 탄화수소 용매하에서 수행하는 것을 특징으로 하는 방법.The process according to claim 1, wherein the polymerization reaction is carried out in aliphatic, cycloaliphatic and aromatic hydrocarbon solvents having 4 to 20 carbon atoms. ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.※ Note: The disclosure is based on the initial application.
KR1019950044343A 1995-11-28 1995-11-28 Method for preparing styrene and butadiene polymer KR100194004B1 (en)

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Application Number Priority Date Filing Date Title
KR1019950044343A KR100194004B1 (en) 1995-11-28 1995-11-28 Method for preparing styrene and butadiene polymer
KR1019980046211A KR100204727B1 (en) 1995-11-28 1998-10-30 Process for the preparation of polybutadiene

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Application Number Priority Date Filing Date Title
KR1019950044343A KR100194004B1 (en) 1995-11-28 1995-11-28 Method for preparing styrene and butadiene polymer

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KR970027125A true KR970027125A (en) 1997-06-24
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KR100408877B1 (en) * 2001-02-09 2003-12-18 이무성 Styrene-diene copolymers by fluorination and sulfonation and its preparation and polymer electrolyte membrane using the said copolymers for fuel cell

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